CN110724299B - 不易收缩热膨胀微胶囊及其应用 - Google Patents
不易收缩热膨胀微胶囊及其应用 Download PDFInfo
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- CN110724299B CN110724299B CN201910866256.3A CN201910866256A CN110724299B CN 110724299 B CN110724299 B CN 110724299B CN 201910866256 A CN201910866256 A CN 201910866256A CN 110724299 B CN110724299 B CN 110724299B
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- acrylate
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 60
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 37
- -1 alkyl vinyl ether Chemical compound 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 150000002825 nitriles Chemical class 0.000 claims abstract description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003607 modifier Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011324 bead Substances 0.000 claims description 6
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229960000834 vinyl ether Drugs 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
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- 239000000853 adhesive Substances 0.000 claims description 4
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 claims description 3
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 claims description 3
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
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- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 claims description 2
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 claims description 2
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 claims description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 2
- UEIPWOFSKAZYJO-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-[2-(2-ethenoxyethoxy)ethoxy]ethane Chemical compound C=COCCOCCOCCOCCOC=C UEIPWOFSKAZYJO-UHFFFAOYSA-N 0.000 claims description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 claims description 2
- RVBFWXYFXKDVKG-UHFFFAOYSA-N 2-ethoxyprop-2-enenitrile Chemical compound CCOC(=C)C#N RVBFWXYFXKDVKG-UHFFFAOYSA-N 0.000 claims description 2
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
本发明公开了一种不易收缩热膨胀微胶囊及其应用，不易收缩热膨胀微胶囊，由外壳和作为芯剂的挥发性溶剂构成，外壳为包括以腈类单体、具有环氧基的单体、丙烯酸酯类单体、烷基乙烯基醚类单体、乙酸乙烯酯单体和咪唑类交联剂为原料，在引发剂的存在下聚合而成的聚合物，重量百分比用量为：腈类单体30～90％、具有环氧基的单体1～50％、丙烯酸酯类单体5～60％、烷基乙烯基醚类单体0～50％、乙酸乙烯酯单体0～50％、咪唑类交联剂0.1～20％、交联剂0.01～5％和引发剂0.01～5％，本发明可作为轻质化材料应用，具有合适的T开始和较高的发泡倍率，具有高耐热性和气体阻隔性，不容易收缩，有更宽的使用温度范围。
Description
技术领域
本发明涉及一种不易收缩热膨胀微胶囊以及应用。
背景技术
热膨胀微胶囊作为轻量化添加剂和表面改性添加剂已经被广泛使用，也可用于发泡油墨、壁纸和以轻量化为目的的塑料或者橡胶中等。
热膨胀微胶囊是由热塑性聚合物为壳内包易挥发物质如脂肪族烃等挥发性溶剂所构成的具有核壳结构的微胶囊。例如，专利ZL201210109302.3中公开了如下方法：由烯属可聚单体和易挥发物质经悬浮聚合得到，该发明主要以丙烯酰胺类单体替代现有技术中甲基丙烯腈单体，获得了具有较高T开始(一般在160℃～200℃)和较高膨胀能力的热膨胀微胶囊。
但是，在一些应用领域中，用户希望供应商所提供的热膨胀微胶囊具有较低的T开始(一般在80℃～160℃)，并且有更好的耐温性能T最大(一般在120℃～200℃)、不易收缩和更宽的使用温度范围。专利ZL201210109302.3中制得的热膨胀微胶囊的性能(主要是T开始和T最大)和耐收缩性能尚不能令用户满意。
因此，提供一种不含生产工艺复杂且价格昂贵甲基丙烯腈、且具有较低的T开始(一般在80℃～160℃)和较高膨胀能力的不易收缩的热膨胀微胶囊成为本发明需要解决的技术问题。
发明内容
本发明的目的在于公开一种不易收缩的热膨胀微胶囊及其应用，以克服现有技术存在的缺陷。
所述的不易收缩热膨胀微胶囊，由外壳和包裹在其内的作为芯剂的挥发性溶剂构成，所述外壳为包括以腈类单体、具有环氧基的单体、丙烯酸酯类单体、烷基乙烯基醚类单体、乙酸乙烯酯和咪唑类交联剂等为起始原料，在引发剂的存在下聚合而成的聚合物；
各个组分的重量百分比用量为：
优选的，各个组分的重量百分比用量为：
所述的腈类单体选自丙烯腈、α-氯丙烯腈、α-乙氧基丙烯腈或富马腈中的一种以上，特别优选为丙烯腈；
所述的具有环氧基的单体选自丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯中的一种以上；
所述的丙烯酸酯类单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、二环戊烯基丙烯酸酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯或异冰片基甲基丙烯酸酯等中的一种以上；
所述的烷基乙烯基醚类单体选自乙基乙烯基醚、丙基乙烯基醚或丁基乙烯基醚等中的一种以上；
所述的咪唑类交联剂包括：
(1)所述2-4-二烷基咪唑，其结构如下(I)所示：
n＝0～20，m＝0-20的整数；
(2)2-烷基咪唑，其结构如下(Ⅱ)所示：
n＝0～20的整数；
(3)2-苯基咪唑，其结构如(Ⅲ)所示：
优选的，所述的咪唑类交联剂选自2-甲基咪唑(2MZ)、2-乙基-4-甲基咪唑(2E4MZ)、2-苯基咪唑(2PZ)、2-十一烷基咪唑(C11Z)或2-十七烷基咪唑(C17Z)等。
优选的，所述的咪唑类交联剂选用具有下列结构式的：2-乙基-4-甲基咪唑：
所述的咪唑类交联剂可采用商业化产品，如湖北信康医药化工有限公司的产品。
所述的交联剂为含有一种或二种以上(含二种)交联性官能团的化合物，具体的，所述的交联剂选自下列化合物中一种或二种以上(含二种)混合物：
二乙烯基苯、乙二醇二(甲基)丙烯酸酯、二(乙二醇)二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1，4-丁二醇二(甲基)丙烯酸酯、1，6-己二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、1，3-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三烯丙基缩甲醛三(甲基)丙烯酸酯、甲基丙烯酸烯丙酯、三羟甲基丙烷三(甲基)丙烯酸酯、三丁二醇二(甲基)丙烯酸酯、PEG#200二(甲基)丙烯酸酯、PEG#400二(甲基)丙烯酸酯、PEG#600二(甲基)丙烯酸酯、3-丙烯酸氧基二醇单丙烯酸酯、三酰基缩甲醛、三烯丙基异氰酸酯、三烯丙基异氰脲酸酯、二乙烯基醚、乙二醇二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚或四乙二醇二乙烯基醚等；
所述的引发剂的选择，现有用于自由基聚合的引发剂(如有机过氧化物或偶氮类化合物等)均适合本发明，具体的引发剂选自下列化合物中一种或二种以上(含二种)混合物：
二(十六烷基)过氧化二碳酸酯、二(4-叔丁基环己基)、过氧化二碳酸酯、过氧化二辛酸、过氧化二苯甲酸、过氧化二月桂酸、过氧化二癸酸、叔丁基过乙酸酯、叔丁基过月桂酸酯、叔丁基过氧化苯甲酸酯、氢过氧化叔丁基、氢过氧化枯烯、乙基过氧化枯烯、二异丙基羟基二羧酸酯、2,2’-偶氮双((2,4-二甲基戊腈)、2,2’-偶氮双(异丁腈)、1,1’-偶氮双(环己烷-1-腈)、二甲基2,2,-偶氮双(2-甲基丙酸酯)或2,2’-偶氮双[2-甲基-N-(2-羟乙基)-丙环氧等；
所述的挥发性溶剂，采用沸点不高于所述的外壳的聚合物软化温度即可，推荐使用C3～C15脂肪族烃类化合物，更优选的易挥发物质是C4～C12直链或支链饱和烃类化合物，进一步优选的易挥发物质是C4～C9直链或支链饱和烃类化合物，作为上述挥发性溶剂，例如，可以列举：丁烷、异丁烷、异戊烷、新戊烷、正己烷、庚烷、异辛烷、辛烷、石油醚等低分子量烃；四甲基硅烷、三甲基乙基硅烷、三甲基异丙基硅烷、三甲基-正丙基硅烷等。其中，优选为丁烷、异丁烷、异戊烷、正己烷、石油醚、异辛烷等。这些挥发性溶剂可以单独使用，也可以并用二种以上，以所提供的可热膨胀微胶囊总重量为100wt％为计算基准，挥发性溶剂占5wt％～50wt％，优选的含量为10wt％～50wt％，进一步优选的含量为15wt％～40wt％，挥发性溶剂的最佳含量为20wt％～35wt％。
优选的，在所述的不易收缩热膨胀微胶囊的外表面还附着有表面改性剂，实现分散性的进一步提高或流动性进一步改善；
所附着的表面改性剂为有机系或无机系改性剂中一种以上，所述有机系改性剂，包括但不限于：硬脂酸镁、硬脂酸钙、硬脂酸锌、硬脂酸钡、硬脂酸锂等金属皂类；聚乙烯蜡、月桂酸酸胺、肉豆寇酸酰胺、棕搁酸酰胺、硬脂酰胺或硬化蓖麻油等合成蜡类；聚丙烯酰胺、聚酰亚胺、尼龙、聚甲基丙烯酸甲酯、聚乙烯或聚四氟乙烯等；所述无机系改性剂，包括但不限于：滑石、云母、膨润土、绢云母、炭黑、二硫化铝、二硫化钨、氟化石墨、氟化钙、氮化硼、二氧化硅、氧化铝、云母、碳酸钙、氢氧化钙、磷酸钙、氢氧化镁、磷酸镁、硫酸钡、二氧化钛、氧化锌、陶瓷珠、玻璃珠或水晶珠等。
对所述表面改性剂的附着量没有特别限定，但如果考虑到可以充分地发挥表面改性剂的功能等，以未附着的可热膨胀性微球总重量为100重量份数计，所述表面改性剂的附着量为0.1-95重量份数，优选为0.5-60重量份数，进一步优选为1-50重量份数，最优选为3-30重量份数。
本发明的制备方法，可采用现有的悬浮聚合方法，如专利ZL201210109302.3报道的方法，在所述的悬浮聚合方法中，可膨胀物质和包括可聚合单体的可聚合化合物通过连续搅拌或添加分散稳定剂(如氢氧化镁或胶体二氧化硅等)而保持悬浮状态，经过悬浮聚合，聚合物能够形成球形。
至于所述的悬浮聚合温度可以根据所用引发剂的种类而定，本发明推荐的悬浮聚合温度为30℃～100℃，优选的悬浮聚合温度为35℃～80℃，更优选的悬浮聚合温度为40℃～70℃。
对于聚合初期压力，优选表压为0～5.0MPa，进而优选0.1～3.0MPa，特别优选0.2～2.0MPa。
本发明的热膨胀性微胶囊的最大发泡温度(Tmax)没有特别限定，优选的范围为120～200℃。上述最大发泡温度小于120℃时，热膨胀性微胶囊的耐热性降低，高温下，容易产生破裂以及收缩，有时无法以高发泡倍率发泡。
本发明人发现，在热膨胀微胶囊中，通过使用含有腈类单体以及具有环氧基的单体和咪唑类交联剂的聚合物，能够具有比较低和较宽的起始发泡温度，并且所得到的热膨胀微胶囊具有高耐热性和气体阻隔性，在使用温度下不容易收缩，有更宽的使用温度范围，从而完成了本发明。
需要说明的是，本说明书中，上述最大发泡温度是指，将热膨胀性微胶囊从常温开始加热的同时测定其直径时、热膨胀性微胶囊达到最大位移量时的温度。
本发明所述的不易收缩热膨胀微胶囊的发泡开始温度(Ts)的优选的范围为80～160℃。
本发明的不易收缩热膨胀微胶囊的体积平均粒径没有特别限定，优选的下限为1μm、优选的上限为50μm。上述体积平均粒径小于1μm时，例如，将热膨胀性微胶囊在基质树脂中配合而成形的情况下，所得到的发泡成形体的气泡过小，有时轻量化变得不充分。上述体积平均粒径超过50μm时，例如，将热膨胀性微胶囊在基质树脂中配合而成形的情况下，所得到的发泡成形体的气泡变得过大，有时在强度等方面成为问题。上述体积平均粒径的更优选的下限为5μm、更优选的上限为45μm。
当聚合基本完成时，可获得水性浆料或分散体的微球，它们可以按原样使用或通过任何常规方法(例如床滤、压滤、叶滤、转滤、带滤或离心进行脱水)而获得所谓的湿滤饼。然而，也可通过任何常规方法(例如喷雾干燥、支架干燥、隧道干燥、旋转干燥、转鼓干燥、通风干燥、涡轮支架干燥、圆盘干燥或流化床干燥等)将该微球干燥。
表面改性剂的附着可以通过混合未附着的可热膨胀性微球和表面改性剂进行。对于混合，没有特别限定，可在具有搅拌装置的容器中进行。另外，也可以使用可进行通常的摇动或搅拌的粉体混合机。作为粉体混合机，例如可以举出带状叶片型混合机、垂直螺旋型混合机等能够进行摇动搅拌或搅拌的粉体混合机。另外，也可以使用近年来通过组合搅拌装置的效率更高的多功能粉体混合机即超级混合机和高速混合机、SV混合机等。
本发明所提供的不易收缩的热膨胀微胶囊，可以作为在轻质化材料，用于造纸、印刷油墨(例如水基油墨、溶剂基油墨、增塑溶胶、紫外固化油墨等)、腻子、密封剂、超轻粘土、底部涂层、粘合剂、粘合剂的脱胶、人造革、真皮、油漆、无纺织物材料、纸和纸板，用于各种材料例如纸、纸板、塑料、金属和织物的涂层(如防滑涂层等)、爆炸物、电缆绝缘层、热塑性塑料(例如聚乙烯、聚氯乙烯和乙烯-乙酸乙烯酯)或热塑性弹性体(例如苯乙烯-乙烯-丁烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、热塑性聚氨酯和热塑性聚烯烃)、丁苯橡胶、天然橡胶、硫化橡胶、硅酮橡胶、热固性聚合物(例如环氧树脂、聚氨酯和聚酯)等领域。
本发明所涉及的原料，如无特别说明，均可采用商业化产品。
本发明的有益效果是：本发明获得的可热膨胀性微胶囊，生产工艺简单，操作条件温和，用环氧类单体代替价格昂贵的甲基丙烯腈，降低了成本；并且获得的微胶囊具有合适的T开始(一般在80℃～160℃)和较高的发泡倍率，并且所得到的热膨胀微胶囊具有高耐热性和气体阻隔性，在使用温度下不容易收缩，有更宽的使用温度范围，在轻质化材料中具有良好的应用。
具体实施方式
下面通过实施例对本发明作进一步阐述。在所列实施例中，除非另有说明，实施例中所有份数和百分率是指以重量计的份数和百分率，及可热膨胀性微胶囊的分析采用下列方法及仪器：
(1)粒径分布特性分析：
热膨胀性微胶囊的粒径分布是通过Bekman coulter公司生产的粒径分布激光衍射分析仪LS13320测量。平均直径测量为体积平均粒径。
(2)发泡特性分析：
热膨胀性微胶囊的特性通过TA Instrument公司生产的热机械分析仪TMA Q-400测量。由直径6.7mm且深度4.5mm的铝盘中容纳的1.0mg热膨胀性微胶囊制备样品。然后，所述铝盘用直径6.5mm且深度4.0mm的铝盘密封。根据TMA扩展探头类型，样品温度以20℃/min的升温速度从环境温度升高至280℃，并由探头施加0.1N的力。分析通过测量探头垂直位移而进行。
-膨胀初始温度(Tstart)：探头位移开始增大时的温度(℃)。
-发泡最高温度(Tmax)：探头位移达到最大时的温度(℃)。
-最大发泡位移((Dmax)：探头位移达到最大时的位移(μm)。
实施例1
制备方法：
(1)将90克丙烯腈、10克甲基丙烯酸缩水甘油酯、12克甲基丙烯酸甲酯、80克丙烯酸甲酯、6克2-乙基-4-甲基咪唑、1.8克过氧化碳酸二环己酯、0.2克三羟甲基丙烷三甲基丙烯酸酯和50克异丁烷混合，获得悬浮聚合的油相；
(2)将280克去离子水、30克氢氧化钠、40克氯化钠和0.2克十二烷基硫酸钠混合，溶解，获得水相A；
将280克去离子水、85克六水合氯化镁和0.01克亚硝酸钠混合充分溶解，获得水相B；
将所述的水相A和所述的水相B混合，获得水相。
油水比为0.35:1(重量)。
将所述的悬浮聚合的油相和所述的水相，通过均质混合机在7000rpm下搅拌2分钟来分散油相和水相，获得悬浮溶液；
将悬浮溶液注入1.5升高压反应釜中，通氮气替换空气，并对反应釜增压以达到0.6MPa的初始压力，然后，在70℃下进行聚合反应20小时，聚合完成后，通过过滤、洗涤、干燥，即可获得得到目标物，所述的不易收缩的热膨胀微胶囊。
实施例2
通过混合160克丙烯腈、2克甲基丙烯酸缩水甘油酯、10克甲基丙烯酸甲酯、18克乙酸乙烯酯、5.7克乙基乙烯基醚、0.2克2-甲基咪唑、0.1克三羟甲基丙烷三甲基丙烯酸酯、4克过氧化苯甲酰、30克异戊烷和30克异辛烷得到悬浮聚合的油相。
在600克离子交换水中，加入23克氯化钠、10克(有效成分量：25％重量)胶体二氧化硅、0.2克十二烷基硫酸钠、0.1克聚乙烯吡咯烷酮以及0.01克亚硝酸钠，然后将pH调节至2.4，均匀地混合，将其作为水性分散介质。油水比为0.41:1(重量)。
通过用均质混合机在6000rpm下搅拌3分钟来分散油相和水相，从而制备悬浮溶液。立刻将悬浮溶液注入1.5升高压反应釜中，通氮气替换空气，并对反应釜增压以达到0.3MPa的初始压力。然后，在70℃下进行聚合反应20小时。聚合完成后，通过过滤、洗涤、干燥得到目标物，所述的不易收缩热膨胀微胶囊。
实施例3～8
除改变所用单体、交联剂、引发剂和易挥发溶剂的种类及用量和聚合物温度外(具体参见表1)，其它条件与实施例1相同，制得不同的不易收缩热膨胀微胶囊，其性能见表2。
比较例1～3
除改变所用单体、交联剂、引发剂和易挥发溶剂的种类及用量和聚合物温度外(具体参见表1)，其它条件与实施例1相同，制得不同的热塑性易挥发微胶囊，其性能见表2。
表1
表1中，AN：丙烯腈，MMA：甲基丙烯酸甲酯，MA:丙烯酸甲酯，BA:丙烯酸丁酯，GMA：甲基丙烯酸缩水甘油酯，VA:乙酸乙烯酯，EVE:乙基乙烯基醚，2MZ：2-甲基咪唑，2E4MZ:2-乙基-4-甲基咪唑，2PZ:2-苯基咪唑，C11Z：2-十一烷基咪唑，C17Z：2-十七烷基咪唑，TMPDMA：三羟甲基丙烷三甲基丙烯酸酯，EGDMA：二甲基丙烯酸乙二醇酯，DEGDE：二乙二醇二乙烯基醚，BPO：过氧化苯甲酰，AIBN：偶氮二异丁腈，LPO：过氧化月桂酰，DCPD：过氧化碳酸二环己酯，IB:异丁烷，IP：异戊烷，NH：正己烷，IO：异辛烷。
表2
由表1和表2可知，和比较例1-3相比，包含具有环氧基的单体和咪唑类交联剂混合物的实施例1-8表现显著改善的耐温性、具有更低T开始和更高的T最大，明显使用温度范围更宽，更不容易收缩和更好的发泡特性。
对比实施例1和比较例1，可以发现比较例1的T开始从80.3℃提高到86.3℃低，而T最大从120.6降低到115.7，同时D最大(μm)
说明当用咪唑类交联剂代替部分AN单体，降低了T开始，而T最大明显提高，同时D最大(μm)也增大，明显使用温度范围更宽，更不容易收缩和更好的发泡特性。因此本发明制备的膨胀微胶囊具有较高的发泡倍率，高耐热性，高的气体阻隔性和在使用温度下不容易收缩的性能。
实施例9
在容器中依次加入上述实施例1得到的膨胀微胶囊2克、粘合剂PT4000 7.5克、分散剂(平平加O)0.5克、保湿剂(甘油)0.3克、交联剂FH 0.5克，用分散搅拌机搅拌均匀，分散搅拌机的搅拌速度为1500转/分，过滤后，加入PTF型增稠剂调节粘度，得到涂层液。
将配制好的涂层液涂敷到布上，涂敷厚度根据不同制品要求调整。涂敷完成后通过50℃烘箱烘干10分钟，然后在温度为120℃下发泡1.5分钟，得到发泡后的涂层高度是原来高度的8倍，手感非常柔软富有弹性的发泡印花效果。
比较例4
除加入上述比较例1得到的膨胀微胶囊2克外，其它配方和工艺条件与实施例9相同，得到发泡后的涂层高度是原来高度的5倍，手感不够柔软和弹性不足的发泡印花效果。
实施例10
将97克聚乳酸(PLA4060)于85℃干燥10h后，在转矩流变仪中以10rpm转速，在135℃条件下与3克上述实施例2得到的热膨胀微胶囊密炼10分钟，得到热膨胀微胶囊与聚乳酸均匀棍合的共混物样品，取出冷却。
将一定质量的上述共混物放入120mm×120mm×4mm模具中，将模具放人平板硫化机内，在185℃和10MPa压力下压制5min，冷却后开模，制得发泡体样品。
比较例5
除加入上述比较例2得到的膨胀微胶囊3克外，其它配方和工艺条件与实施例10相同，制得发泡体样品。
实施例10和比较例5性能评价方式如下：
发泡样品密度按照GB/T 6343-2009测定。常温下，导热系数使用导热系数测量仪测定。冲击强度按照ASTM D256测定，样条尺寸为64mm×12.8mm×4mm。弯曲性能按照GB/T9341-2000测定，样条尺寸为80mm×10mm×4mm，跨度为60mm，试验速度为2mm/min。
实施例10及比较例5性能测试结果见下表：
表3
从表3的性能数据可见：从实施例10与比较例5的对比可以看出，本发明的实施例2热膨胀微胶囊填充聚乳酸材料在各项性能与比较例2基本相同的前提下，材料密度明显减少，相同体积的成品制件重量可以减轻25.9％，室温下，发泡体的导热系数从0.096W/(m·K)减小到0.073W/(m·K)，说明热阻隔性明显提升。
从上述应用结果，进一步说明包含具有环氧基的单体和咪唑类交联剂混合物的热膨胀微胶囊具有较高的发泡倍率，高耐热性，高的气体阻隔性和在使用温度下不容易收缩的性能。
以上内容仅为本发明的较佳实施例，对于本领域的普通技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，本说明书内容不应理解为对本发明的限制。
Claims (13)
1.不易收缩热膨胀微胶囊，其特征在于，由外壳和包裹在其内的作为芯剂的挥发性溶剂构成，所述外壳为包括以腈类单体、具有环氧基的单体、丙烯酸酯类单体、烷基乙烯基醚类单体、乙酸乙烯酯单体和咪唑类交联剂为起始原料，在引发剂的存在下聚合而成的聚合物，各个组分的重量百分比用量为：
所述的交联剂选自下列化合物中一种或二种以上混合物：
二乙烯基苯、乙二醇二(甲基)丙烯酸酯、二(乙二醇)二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、甲基丙烯酸烯丙酯、三羟甲基丙烷三(甲基)丙烯酸酯、三丁二醇二(甲基)丙烯酸酯、PEG#200二(甲基)丙烯酸酯、PEG#400二(甲基)丙烯酸酯、PEG#600二(甲基)丙烯酸酯、三烯丙基异氰脲酸酯、二乙烯基醚、乙二醇二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚或四乙二醇二乙烯基醚；
所述的咪唑类交联剂包括：
(1)2,4-二烷基咪唑，其结构如下(I)所示：
n＝0～20，m＝0-20的整数；
(2)2-烷基咪唑，其结构如下(Ⅱ)所示：
n＝0～20的整数；
(3)2-苯基咪唑，其结构如(Ⅲ)所示：
2.根据权利要求1所述的不易收缩热膨胀微胶囊，其特征在于，各个组分的重量百分比为：
3.根据权利要求1或2所述的不易收缩热膨胀微胶囊，其特征在于，所述的腈类单体选自丙烯腈、α-氯丙烯腈、α-乙氧基丙烯腈或富马腈中的一种以上。
4.根据权利要求1或2所述的不易收缩热膨胀微胶囊，其特征在于，所述的具有环氧基的单体选自丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯中的一种以上。
5.根据权利要求1或2所述的不易收缩热膨胀微胶囊，其特征在于，所述的丙烯酸酯类单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、二环戊烯基丙烯酸酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯或异冰片基甲基丙烯酸酯中的一种以上。
6.根据权利要求1或2所述的不易收缩热膨胀微胶囊，其特征在于，所述的烷基乙烯基醚类单体选自乙基乙烯基醚、丙基乙烯基醚或丁基乙烯基醚中的一种以上。
7.根据权利要求1所述的不易收缩热膨胀微胶囊，其特征在于，所述的咪唑类交联剂选自2-甲基咪唑(2MZ)、2-乙基-4-甲基咪唑(2E4MZ)、2-苯基咪唑(2PZ)、2-十一烷基咪唑(C11Z)或2-十七烷基咪唑(C17Z)。
8.根据权利要求7所述的不易收缩热膨胀微胶囊，其特征在于，所述的咪唑类交联剂选用2-乙基-4-甲基咪唑。
9.根据权利要求1或2所述的不易收缩热膨胀微胶囊，其特征在于，所述的引发剂选自下列化合物中一种或二种以上(含二种)混合物：
二(十六烷基)过氧化二碳酸酯、叔丁基过氧化苯甲酸酯、氢过氧化叔丁基、氢过氧化枯烯、乙基过氧化枯烯、2,2’-偶氮双(2,4-二甲基戊腈)、2,2’-偶氮双(异丁腈)、1,1’-偶氮双(环己烷-1-腈)。
10.根据权利要求1或2所述的不易收缩热膨胀微胶囊，其特征在于，所述的挥发性溶剂，采用沸点不高于所述的外壳的聚合物软化温度的化合物。
11.根据权利要求1或2所述的不易收缩热膨胀微胶囊，其特征在于，在所述的不易收缩热膨胀微胶囊的外表面还附着有表面改性剂。
12.根据权利要求11所述的不易收缩热膨胀微胶囊，其特征在于，所附着的表面改性剂为有机系或无机系改性剂中一种以上，所述有机系改性剂，包括：硬脂酸镁、硬脂酸钙、硬脂酸锌、硬脂酸钡、硬脂酸锂；肉豆寇酸酰胺、硬脂酰胺或硬化蓖麻油；聚丙烯酰胺、聚酰亚胺、尼龙、聚甲基丙烯酸甲酯、聚乙烯或聚四氟乙烯；所述无机系改性剂，包括：滑石、云母、膨润土、绢云母、炭黑、二硫化钨、氟化石墨、氟化钙、氮化硼、二氧化硅、氧化铝、碳酸钙、氢氧化钙、磷酸钙、氢氧化镁、磷酸镁、硫酸钡、二氧化钛、氧化锌、陶瓷珠、玻璃珠或水晶珠。
13.根据权利要求1～12任一项所述的不易收缩热膨胀微胶囊的应用，其特征在于，作为轻质化材料，用于造纸、印刷油墨、腻子、密封剂、超轻粘土、底部涂层、粘合剂、粘合剂的脱胶、人造革、真皮、油漆、无纺织物材料、纸、纸板、塑料、金属和织物的涂层、爆炸物、电缆绝缘层、热塑性弹性体、丁苯橡胶、天然橡胶、硫化橡胶、硅酮橡胶、热固性聚合物领域。
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